Carbonyl compound and process of preparing the same



Io Drawing.

hydes.

Patented 1930 umrso STATES. PATENT orrlcr.

-- a. ms or narom, imw messy, assumes. no srn'mann comm, a coaromrron on nnmwaan OIL DEVEI-Ol I OABBONYLGOHIROUND PROGESSOI' PREPARING THE This invention relates to improvements in by way of' illustrationto the treatment of.

petroleum oil for the production of the 'gher aldehydes.

have found that aldehydes may be economically prepared from etroleum hydrocarbons, for example straig t-run or cracked gasoline, by a series of reactions including the roduction of olefins, the conversion of the efins into chlorhydrins, and the transformation of the chlorhydrins into alde- The olefins may be produced by passing the hydrocarbon stock in vapor form through a heated zone, together with a regulated amount of air or oxygen. The stock is preferabl gasolirie, but may be any pe troleum hy rocarbon mixture containing no jected at a rate of about 5' to cu ic feet' substantial amount of components heavier than those normally occurring in kerosene. When air is used it should or 'naril be inper pound of hydrocarbon. The tempera-' ture is ke t below the usual of about 25 to 875 F. Temperatures between 300 and 6503- F. are generally-suit.-

able for my purpose.

Steam may be introduced as a temperature modifier, or for other purposes, if desired. Steam injection is particularly useful if undiluted oxygen instead of air is employed. Atmospheric'pressure is recom-' mended, except for stocks of high vaporizing temperature. With such stocks it is often desirable to reduce the pressure to an amount suflicient to ensure vaporiza,tion without cracking.

From the heated zone the vasors. pass. to a condenser system. When esired, the products may be treated to remove any gumcracking range.

Application fled February 27, 1928 Serial No. 91,280..

forming constituents that may be present. Washing with water, or with an acid or alkali solution, or steaming, are suitable in this connection.

The method of preparin olefins does not form an essential [part of t e present invention, and any ot er suitable method may be substituted for that given above. The product prepared as described, or in a similar manner, will contain substantial uantities of the normal hydrocarbons of t e olefin series especially pentyleiie and the members of' the olefin/series up "to and including decylene. Unsaturated compounds of great er complexity may also be formed in small amount. These are not detrimental for most purposes, but the simpler olefins are of chief im ortance for'my purpose.

some cases gasoline prepared by cracking methods contains asufficient amount of olefin material to make it directly suitable for treatment by my process. In accordance with the present invention, the olefins are first converted into chlorhydrins. The method consists in stirring the olefins at low temperature, say-about 0 (3., with adilute solution ofhypochlorous-acid; As a rule,

Ill

the hypochlorous acid solution should not be stronger than 1%, if formation of dichlorids is to be avoided. However, in my process the chlorhydrins form only an intermediate roduct and, are later transformed into alehydes b heating with water. Dichlorids are there ore not objectionable, since they react similarly to the chlorhydrins when so treated. This is an advantageous feature of the process since no precaution need be taken to avoid e the chlorinating method described: is

the formation of dichloride: Higher and more reactive concentrations of v preferred, any method which' furnishes chlorhydrins, or mixtures ofchlo'rhydr'insf and dichlorids, will serve. I use the term chlorhydrin. as meaning a glycol esterof hydrochloric acid Selecting nonylene as illustrative of the olefins being treated, the reactions for the formation of chlorhydrin and dichlorid may take place as represented by the following equations:

O H15-CH CH2 C,H15.CHOH.OH2O1 1 C7H15CH v C H15.CHCl.GH2Cl (II).

tact and heated to about 110 to 200 C.

for a period of about one tothree hours'in a closed vessel. The following equations are illustrative of the type of reaction that may take place:

C H .CHOH.GH Cl H O v o.H...oH2.oHo Ho1+ H O (III) C1H15-GHCl-CH G1+ H2O 0 H, .CHOH.CH Cl HCl (IV C,H1' .OHOH.CH2C1+ H O C- H .CH .CHO H01 H O (IV The higher aldehydes have heretofore been made only by laborious and costly methods. They may be prepared economically and in a state of substantial urity by the process disclosed herein; Fractionation under vacuum sufiicies' to separate the aldehydes from unchanged chlorhydrins, dichlorids, and other compounds that may be present. The aldehydes are useful as starting materials for the preparation of a wide variety of compounds and are valuable. in themselves as fixatives in the perfume industry and forother purposes.

I If the double bond of the olefin is not at the end of the hydrocarbon chain, then a ketone is obtained by heating the correspondingchlorhydrin' derivative with water. However,'my experiments show that the olefins obtained by the above described oxidation process, or in crackin contain the double bond mostly at the en of the hydrocarbonchain. Therefore, only an inconsiderable amount of ketones is formed.

' pared directly in the fuel.

An important feature of my invention is the improvement of motor fuel by addition of aldehyde material. For this purpose the aldehydes may be prepared separately and blended with the fuel, or they may be pre- For' example, when a cracked gasoline containing a relatively high percentage of olefin material is are formed, and convertin treated with hypoehlorous acid or other suitable chlorinatmg agent for the production of chlorhydrins, and with water for the proT duction of aldehydes, as decribed above, a gasoline of much improved character is obtained. It has a pleasant odor and a substantially less tendency to produce knocking or detonation than the untreated gasoline.

The aldehydes have, as a rule, a higher boiling point than the hydrocarbons from which they are formed. There is accordingly some elevation of the boiling point range of the fuel, but this is not an important objection, since the increase of boiling point range may be compensated for by the addition of lighter gasoline, which will be retained on account of the high fixative power of the aldehydes. Ordinarily, carbonyl compounds, whether aldehydes or ketones, are suitable as an anti-knock agent in motor fuel.

It will be. understood that my invention is not restricted by any theoretical considerations in the foregoing description and that various "changes and alternative procedures may-be adopted within the scope of the appended claims, in which it is my intention to claim all novelty inherent in the invention as broadly as the prior art permits.

I claim:

- 1. Process of preparing carbonyl compounds of h drocarbons, comprising treating olefins o butylene with hypoehlorous acid, whereby chlorin-containing compounds are formed, and transforming the chlorin-containing compounds into carbonyl compounds by heating with water.

2. Process of preparing aldehydes from hydrocarbons liquid atroom temperature and having a molecular weight not greater greater molecular weight than than that of hydrocarbons normally present kerosene, comprisin converting at least a portion of said hy rocarbons into olefins, treating the olefins w th hypoehlorous acid, whereby chlorhydrms the chlorhydrins into aldeh des by heatlng with water.

3. Process of orming carbonyl derivatives of hydrocarbon compounds in a mixture of olefin and non-olefin hydrocarbons liquid at room temperature and having a molecular weight not greater than that of hydrocarbons normally present in kerosene, comprlsing treating the mixture with a chlormatmg in gasoline and agent to convert the olefins into chlorin-conv taining compounds, and converting the chlorin-containing compounds into carbonyl compounds by heatlng with water.

4. Process offorming aldehydes in a gasoline containing olefins, comprising treating I the gasoline with hypoehlorous acid, and converting the resulting chlorinated substances into aldehydes by hea-tmg with water.

.STEPHENA. KISS. 

